scholarly journals Frustrated Lewis pairs in ionic liquids and molecular solvents – a neutron scattering and NMR study of encounter complexes

2018 ◽  
Vol 54 (63) ◽  
pp. 8689-8692 ◽  
Author(s):  
Lucy C. Brown ◽  
James M. Hogg ◽  
Mark Gilmore ◽  
Leila Moura ◽  
Silvia Imberti ◽  
...  
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Neutron Scattering ◽  
Frustrated Lewis Pairs ◽  
Frustrated Lewis Pair ◽  
Nmr Study ◽  
Molecular Solvents ◽  
Lewis Pairs

Encounter complexes of a frustrated lewis pair are more stable and prevalent in an ionic liquid than in benzene.

Bis(perchlorocatecholato)silane and Heteroleptic Bidonors: Hidden Frustrated Lewis Pairs by Ring Strain

2021 ◽  
Author(s):  
Deborah Hartmann ◽  
Sven Braner ◽  
Lutz Greb
Keyword(s):  
Ammonia Borane ◽  
Frustrated Lewis Pairs ◽  
Ring Strain ◽  
Frustrated Lewis Pair ◽  
Lewis Pairs

Bis(perchlorocatecholato)silane and bidentate N,N- or N,P-heteroleptic donors form hexacoordinated complexes. Depending on the ring strain and hemilability in the adducts, Frustrated Lewis pair reactivity with aldehydes and catalytic ammonia borane...

scholarly journals Reversible O–H bond activation by an intramolecular frustrated Lewis pair

2019 ◽  
Vol 48 (9) ◽  
pp. 2896-2899 ◽  
Author(s):  
Petra Vasko ◽  
M. Ángeles Fuentes ◽  
Jamie Hicks ◽  
Simon Aldridge
Keyword(s):  
Bond Activation ◽  
Frustrated Lewis Pairs ◽  
Frustrated Lewis Pair ◽  
Lewis Pairs

The interactions of the O–H bonds in alcohols, water and phenol with dimethylxanthene-derived frustrated Lewis pairs (FLPs) have been probed.

Metal-Free Iodoperfluoroalkylation: Photocatalysis versus Frustrated Lewis Pair Catalysis

Synthesis ◽  
2020 ◽  
Vol 53 (01) ◽  
pp. 123-134
Author(s):  
Constantin Czekelius ◽  
Lucas Helmecke ◽  
Michael Spittler ◽  
Bernd M. Schmidt
Keyword(s):  
Visible Light ◽  
Visible Light Irradiation ◽  
Light Irradiation ◽  
Reaction Pathways ◽  
Frustrated Lewis Pairs ◽  
Metal Free ◽  
Comprehensive Account ◽  
Frustrated Lewis Pair ◽  
Catalytic Metal ◽  
Lewis Pairs

A comparison of two catalytic, metal-free iodoperfluoro­alkylation protocols is presented. Frustrated Lewis pairs [ t Bu3P/B(C6F5)3] or phosphines/phosphites under visible light irradiation efficiently mediate the functionalization of non-activated alkenes and alkynes. A comprehensive account of the corresponding substrate scopes as well as insights into the mechanistic details of both reaction pathways are provided.

Plasmonic behavior of ionic liquid stabilized gold nanoparticles in molecular solvents

2017 ◽  
Vol 41 (21) ◽  
pp. 12989-12995 ◽  
Author(s):  
Sachin Thawarkar ◽  
Balu Thombare ◽  
Nageshwar D. Khupse
Keyword(s):  
Gold Nanoparticles ◽  
Ionic Liquid ◽  
Ionic Liquids ◽  
Surface Plasmon Resonance ◽  
Dielectric Properties ◽  
Surface Plasmon ◽  
Plasmon Resonance ◽  
Facile Synthesis ◽  
Imidazolium Ionic Liquids ◽  
Molecular Solvents

In this paper, we have demonstrated the facile synthesis of stable gold nanoparticles (AuNPs) using imidazolium ionic liquids (ImILs) as a stabilizer as well as a surfactant and their surface plasmon resonance (SPR) in different molecular solvents with varying dielectric properties.

scholarly journals Tuning Activity and Selectivity During Alkyne Activation by Gold(I)/Platinum(0) Frustrated Lewis Pairs

2020 ◽  
Author(s):  
Nereida Hidalgo ◽  
Juan Jose Moreno ◽  
Marina Pérez-Jiménez ◽  
Celia Maya ◽  
Joaquin López-Serrano ◽  
...  
Keyword(s):  
Transition Metals ◽  
Computational Analysis ◽  
Product Distribution ◽  
Frustrated Lewis Pairs ◽  
Cooperative Action ◽  
Frustrated Lewis Pair ◽  
Frustrated Systems ◽  
Selection Of ◽  
Lewis Pairs

Introducing transition metals into frustrated Lewis pair systems has attracted considerable attention in recent years. Here we report a selection of three metal-only frustrated systems based on Au(I)/Pt(0) combinations and their reactivity towards alkynes. We have inspected the activation of the simplest alkyne, namely acetylene, as well as of other internal and terminal triply bonded hydrocarbons. The gold(I) fragments are stabilized by three bulky phosphines bearing terphenyl groups. We have observed that subtle modifications on the substituents of these ligands proved critical to control the regioselectivity of acetylene activation and the product distribution resulting from C(sp)—H cleavage of phenylacetylene. A mechanistic picture based on experimental observations and computational analysis is provided. As a result of the cooperative action of the two metals of the frustrated pairs, several uncommon heterobimetallic structures have been fully characterized.

scholarly journals Tuning Activity and Selectivity During Alkyne Activation by Gold(I)/Platinum(0) Frustrated Lewis Pairs

2020 ◽  
Author(s):  
Nereida Hidalgo ◽  
Juan Jose Moreno ◽  
Marina Pérez-Jiménez ◽  
Celia Maya ◽  
Joaquin López-Serrano ◽  
...  
Keyword(s):  
Transition Metals ◽  
Computational Analysis ◽  
Product Distribution ◽  
Frustrated Lewis Pairs ◽  
Cooperative Action ◽  
Frustrated Lewis Pair ◽  
Frustrated Systems ◽  
Selection Of ◽  
Lewis Pairs

Introducing transition metals into frustrated Lewis pair systems has attracted considerable attention in recent years. Here we report a selection of three metal-only frustrated systems based on Au(I)/Pt(0) combinations and their reactivity towards alkynes. We have inspected the activation of the simplest alkyne, namely acetylene, as well as of other internal and terminal triply bonded hydrocarbons. The gold(I) fragments are stabilized by three bulky phosphines bearing terphenyl groups. We have observed that subtle modifications on the substituents of these ligands proved critical to control the regioselectivity of acetylene activation and the product distribution resulting from C(sp)—H cleavage of phenylacetylene. A mechanistic picture based on experimental observations and computational analysis is provided. As a result of the cooperative action of the two metals of the frustrated pairs, several uncommon heterobimetallic structures have been fully characterized.

Bis(pentafluorophenyl)phenothiazylborane – A Pseudo Frustrated Radical Pair for the Catalytic Dehydrocoupling of Stannanes

2020 ◽  
Author(s):  
Jordan N. Bentley ◽  
Ekadashi Pradhan ◽  
Tao Zeng ◽  
Christopher B. Caputo
Keyword(s):  
Small Molecules ◽  
Computational Analysis ◽  
Bond Activation ◽  
Radical Pair ◽  
Frustrated Lewis Pairs ◽  
Frustrated Lewis Pair ◽  
Lewis Pairs

The understanding of the mechanism by which frustrated Lewis pairs activate small molecules has been evolving with the discovery that both heterolytic and homolytic bond activation is possible. Herein we characterized a novel Lewis acidic aminoborane containing a phenothiazyl substituent and demonstrate its potential to catalytically promote the dehydrocoupling of tin hydrides. The reactivity observed implies this species promotes homolytic bond activation, however computational analysis suggests a heterolytic mechanism for this reaction. This result represents the first frustrated Lewis pair system to blur the lines between heterolytic and homolytic reactivity.

scholarly journals Exploiting the Electronic Tuneability of Carboranes as Supports for Frustrated Lewis Pairs

Molecules ◽  
2018 ◽  
Vol 23 (12) ◽  
pp. 3099 ◽  
Author(s):  
Amanda Benton ◽  
Zachariah Copeland ◽  
Stephen M. Mansell ◽  
Georgina M. Rosair ◽  
Alan J. Welch
Keyword(s):  
Lewis Acid ◽  
Michael Addition ◽  
Coupling Constants ◽  
Frustrated Lewis Pairs ◽  
Acid Component ◽  
Frustrated Lewis Pair ◽  
Lewis Pairs

The first example of a carborane with a catecholborolyl substituent, [1-Bcat-2-Ph-closo-1,2-C2B10H10] (1), has been prepared and characterized and shown to act as the Lewis acid component of an intermolecular frustrated Lewis pair in catalyzing a Michael addition. In combination with B(C6F5)3 the C-carboranylphosphine [1-PPh2-closo-1,2-C2B10H11] (IVa) is found to be comparable with PPh2(C6F5) in its ability to catalyze hydrosilylation, whilst the more strongly basic B-carboranylphosphine [9-PPh2-closo-1,7-C2B10H11] (V) is less effective and the very weakly basic species [μ-2,2ʹ-PPh-{1-(1ʹ-1ʹ,2ʹ-closo-C2B10H10)-1,2-closo-C2B10H10}] (IX) is completely ineffective. Base strengths are rank-ordered via measurement of the 1J 31P-77Se coupling constants of the phosphineselenides [1-SePPh2-closo-1,2-C2B10H11] (2), [9-SePPh2-closo-1,7-C2B10H11] (3), and [SePPh2(C6F5)] (4).

Towards solvent-controlled reactivity in ionic liquids

2013 ◽  
Vol 85 (10) ◽  
pp. 1979-1990 ◽  
Author(s):  
Hon Man Yau ◽  
Sinead T. Keaveney ◽  
Bradley J. Butler ◽  
Eden E. L. Tanner ◽  
Max S. Guerry ◽  
...  
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Mole Fraction ◽  
Reaction Coordinate ◽  
Ionic Solvent ◽  
Molecular Solvents

Ionic liquids are frequently touted as alternatives to traditional molecular solvents but are limited in their applicability as the outcome of reactions may be altered on moving from a molecular to an ionic solvent. This manuscript summarizes our progress towards a predictive framework through understanding how ionic solvents affect organic processes, with an emphasis on how these findings might be applied. Particularly, we will consider the importance of the mole fraction of the ionic liquid used, including some hitherto undisclosed results, as well as the importance of understanding the key interactions of the solvent with the components along the reaction coordinate.

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